KR102601673B1 - Curable resin composition and cured film - Google Patents

Abstract

Resin (A), which is a copolymer comprising a structural unit (Aa) having an α,β-unsaturated carbonyl group and a structural unit (Ab) having an active methylene group or an active methine group;
At least one compound selected from the group consisting of quaternary ammonium salts, quaternary phosphonium salts, and tertiary sulfonium salts,
At least one compound selected from the group consisting of epoxy compounds and 5-membered ring carbonate compounds
A curable resin composition comprising:

Description

Curable resin composition and cured film {CURABLE RESIN COMPOSITION AND CURED FILM}

The present invention relates to a curable resin composition and a cured film formed from the curable resin composition.

In the examples of Japanese Patent Application Laid-Open No. 3-172301, methyl methacrylate, ethyl methacrylate, and methacrylic acid were polymerized, and then the reaction product of glycidyl methacrylate was used as a resin component. A composition comprising the composition and a cured film obtained by curing the composition at 230° C. are described.

The present invention includes the following.

[1] Resin (A), which is a copolymer containing a structural unit (Aa) having an α, β-unsaturated carbonyl group and a structural unit (Ab) having an active methylene group or an active methine group,

At least one compound selected from the group consisting of quaternary ammonium salts, quaternary phosphonium salts, and tertiary sulfonium salts (hereinafter, the compound is referred to as the “first additive”),

At least one compound selected from the group consisting of epoxy compounds and 5-membered ring carbonate compounds (hereinafter, the compound is referred to as the “second additive”)

A curable resin composition comprising:

[2] The curable resin composition according to [1], comprising a quaternary ammonium salt and an epoxy compound.

[3] The curable resin composition according to [1] or [2], wherein the epoxy compound is an epoxy compound having at least two oxiranyl groups in one molecule.

[4] A cured film formed from the curable resin composition according to any one of [1] to [3].

In this specification, the compounds exemplified as each component can be used individually or in combination of multiple types, unless otherwise specified.

[Curable resin composition]

The curable resin composition of the present invention contains a resin (hereinafter referred to as resin (A)), a first additive, and a second additive. The curable resin composition of the present invention may further contain a solvent (hereinafter referred to as solvent (E)).

Resin (A) includes a structural unit having an α,β-unsaturated carbonyl group (hereinafter referred to as structural unit (Aa)) and a structural unit having an active methylene group or an active methine group (hereinafter referred to as structural unit (Ab). ) is a copolymer containing

The first additive is at least one compound selected from the group consisting of quaternary ammonium salts, quaternary phosphonium salts, and tertiary sulfonium salts.

The second additive is at least one compound selected from the group consisting of epoxy compounds and 5-membered ring carbonate compounds.

By allowing the resin (A) to coexist with the first additive and the second additive, the resulting cured film has excellent solvent resistance.

The curable resin composition of the present invention may contain a polymerizable compound (hereinafter referred to as polymerizable compound (C)). When the polymerizable compound (C) is included, it is preferable to also include a polymerization initiator (hereinafter referred to as polymerization initiator (D)).

The curable resin composition of the present invention contains other components, such as a polymerization initiation aid (hereinafter referred to as polymerization initiation aid (H)), a leveling agent (hereinafter referred to as leveling agent (B)), and a colorant. (hereinafter referred to as colorant (K)) may be included.

<Resin (A)>

Resin (A) has a structural unit (Aa) and a structural unit (Ab). Resin (A) may further contain other structural units (hereinafter referred to as structural units (Ac)).

Resin (A) may contain two or more types of structural units (Aa) and structural units (Ab).

Resin (A) is preferably an alkali-soluble resin. Alkali solubility refers to the property of dissolving in a developer solution, which is an aqueous solution of an alkaline compound. The resin (A) preferably contains a structural unit (hereinafter referred to as structural unit (Ac1)) having an acid group as the structural unit (Ac). The resin (A) may include a structural unit (hereinafter referred to as structural unit (Ac2)) other than the structural unit (Ac1) as the structural unit (Ac). Hereinafter, each structural unit will be described in detail.

In addition, in this specification, “(meth)acrylic acid” refers to at least one compound selected from the group consisting of acrylic acid and methacrylic acid. Notations such as “(meth)acryloyl” and “(meth)acrylate” also have the same meaning.

〔1〕 Composition unit (Aa)

In the present specification, the α,β-unsaturated carbonyl group has a structure represented by -CO-CX=CX- (X independently represents an arbitrary substituent), and is preferably -CO-CX=CH-. Examples of

The structural unit (Aa) is, for example, a structural unit having a carboxyl group (hereinafter referred to as structural unit (Aa')) and a compound having an α,β-unsaturated carbonyl group (hereinafter referred to as a carboxylic acid reactive compound). ) is obtained by adding. Examples of the carboxylic acid-reactive compound include compounds having an oxiranyl group and an α,β-unsaturated carbonyl group (hereinafter referred to as monomer (Aa'')). Examples of the structural unit (Aa') include structural units having a carboxyl group among the structural units (Ac1) described later.

The structural unit (Aa) can also be obtained, for example, by reacting (meth)acrylic acid with a structural unit having an oxiranyl group.

As the monomer (Aa''), a compound having a structure in which a straight-chain or branched unsaturated aliphatic hydrocarbon is epoxidized and an α,β-unsaturated carbonyl group (hereinafter referred to as monomer (Aa''-1)) and an unsaturated Examples include compounds having an epoxidized alicyclic hydrocarbon structure and an α,β-unsaturated carbonyl group (hereinafter referred to as monomer (Aa''-2)).

Examples of the monomer (Aa''-1) include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, glycidyl itaconic acid, etc. I can hear it.

As a specific example of the monomer (Aa''-2),

3,4-epoxycyclohexylmethyl (meth)acrylate,

5,6-epoxytricyclo[5.2.1.0 ^2,6 ]decan-8-yl(meth)acrylate,

5,6-epoxytricyclo[5.2.1.0 ^2,6 ]decan-8-yl oxymethyl (meth)acrylate,

2,3-epoxycyclopentylmethyl (meth)acrylate,

2-hydroxy-3-(2,3-epoxycyclopentyloxy)cyclopentylmethyl(meth)acrylate,

3-(3,4-epoxycyclohexylmethyloxycarbonyl)-6-hydroxycyclohexylmethyl (meth)acrylate,

2-hydroxy-5-(3,4-epoxycyclohexylcarbonyloxymethyl)cyclohexylmethyl(meth)acrylate,

3-(3,4-epoxycyclohexyl)-9-hydroxy-1,5-dioxaspiro[5,5]undecan-8-yl(meth)acrylate,

3-(3,4-epoxycyclohexyl)-9-hydroxy-2,4-dioxaspiro[5,5]undecan-8-yl(meth)acrylate,

etc. can be mentioned. These can be used individually, or two or more types can be used together. Among these, glycidyl (meth)acrylate or 3,4-epoxycyclohexylmethyl (meth)acrylate is suitably used.

For example, the structural unit (Aa) obtained by adding 3,4-epoxycyclohexylmethyl (meth)acrylate to the (meth)acrylic acid structural unit is represented by the formula (Aa-1).

[In formula (Aa-1), R ¹ and R ^x independently represent a hydrogen atom or a methyl group.]

For example, a structural unit obtained by adding glycidyl (meth)acrylate to a (meth)acrylic acid structural unit is represented by the formula (Aa-2).

[In formula (Aa-2), R ⁵ and R ^y independently represent a hydrogen atom or a methyl group.]

As the structural unit (Aa), a structural unit represented by the formula (Aa-1) or a structural unit represented by the formula (Aa-2) is preferable.

〔2〕 Constituent unit (Ab)

Examples of the structural unit (Ab) include structural units derived from unsaturated compounds having an active methylene group or an active methine group. The structural unit derived from an unsaturated compound having an active methylene group or an active methine group means a structural unit derived from the unsaturated compound obtained by polymerizing the unsaturated compound.

Examples of the unsaturated compound having an active methylene group from which the structural unit (Ab) is derived include a compound represented by formula (I), and examples of an unsaturated compound having an active methine group include a compound represented by formula (II).

[In formula (I) and formula (II),

R ¹¹ represents a group represented by any of formulas (1-1) to (1-4).

R ¹² represents a single bond, -X- or -XO-* (* represents the bond with R ¹³ ).

R ¹³ represents -CO- or -SO ₂ -.

R ¹⁴ represents -CO-R ¹⁵ , -SO ₂ -R ¹⁵ , a cyano group, or a nitro group.

X represents a divalent hydrocarbon group having 1 to 20 carbon atoms.

R ¹⁵ represents a hydrocarbon group with 1 to 24 carbon atoms or an alkoxy group with 1 to 12 carbon atoms.]

[In formulas (1-1) to (1-4), R ¹⁶ and R ¹⁸ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms.

R ¹⁷ represents a hydrocarbon group having 1 to 24 carbon atoms, and the methylene group contained in the hydrocarbon group may be substituted with -CO- or -O-.]

Examples of the hydrocarbon group having 1 to 24 carbon atoms for R ¹⁵ to ^{R 18} include alkyl groups such as methyl, ethyl, propyl, butyl, and hexyl; Cycloalkyl groups, such as cyclohexyl group, etc. are mentioned.

When the methylene group contained in the hydrocarbon group for R ¹⁷ is substituted by -O- or -CO-, the hydrocarbon group has 2 to 24 carbon atoms. Examples of the group in which the methylene group contained in the hydrocarbon group of the hydrocarbon group having 2 to 24 carbon atoms is substituted with -O- or -CO- include alkoxy groups such as methoxy group, ethoxy group, propoxy group, and hexyloxy group; Cycloalkoxy groups such as cyclohexyloxy groups; and oxo-containing hydrocarbon groups such as 2,4-dioxopentyl group, 3,5-dioxohexyl group, and 1,3-dioxobutyloxyethyl group.

The divalent hydrocarbon group having 1 to 20 carbon atoms for A divalent chain aliphatic hydrocarbon group; divalent cyclic aliphatic hydrocarbon groups having 3 to 20 carbon atoms, such as cyclohexanediyl group, tricyclodecanediyl group, and groups represented by the following formula; Examples include divalent aromatic hydrocarbon groups having 6 to 20 carbon atoms, such as phenylene groups, and preferably methylene groups or ethylene groups.

R ¹¹ is preferably a group represented by formula (1-1) or formula (1-4), and more preferably a group represented by formula (1-1).

R ¹² represents a single bond, -X- or -XO-* (* represents a bond with R ¹³ ), and preferably X is a divalent saturated hydrocarbon group having 1 to 12 carbon atoms.

R ¹³ is preferably -CO-.

R ¹⁴ is preferably -CO-R ¹⁵ .

R ¹⁵ is preferably an alkyl group with 1 to 6 carbon atoms or an alkoxy group with 1 to 6 carbon atoms, and more preferably an alkyl group with 1 to 6 carbon atoms.

R ¹⁶ is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and more preferably a hydrogen atom or a methyl group.

R ¹⁷ is preferably an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 3 to 12 carbon atoms.

R ¹⁸ is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and more preferably a hydrogen atom.

Specific examples of the compound represented by formula (I) include the following compounds.

Specific examples of the compound represented by formula (II) include the following compounds.

Compounds represented by any of Formulas (I-1) to Formula (I-7), Formula (I-16), Formula (II-1) and Formula (II-2) have R ¹¹ represented by Formula (1-1) ) and R ¹⁶ is a methyl group. However, compounds in which the methyl group at R ¹⁶ is replaced with a hydrogen atom can also be used as compounds that lead to the structural unit (Ab).

The structural unit (Ab) is preferably a structural unit represented by the formula (Ab-1).

[In formula (Ab-1), R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.]

Examples of the alkyl group having 1 to 6 carbon atoms for R ⁴ include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl and n-hexyl groups. can be mentioned.

R ⁴ preferably includes a hydrogen atom and a methyl group.

As a compound deriving the structural unit represented by formula (Ab-1), for example, 2-(1,3-dioxobutyloxy)ethyl (meth)acrylate [compound represented by formula (I-1) ] can be mentioned.

〔3〕 Composition unit (Ac1)

The structural unit (Ac1) is a structural unit derived from an unsaturated compound having an acid group. Examples of acid groups include carboxyl groups, phenolic hydroxy groups, and sulfo groups. The unsaturated compound having two or more carboxyl groups may be an acid anhydride. The structural unit derived from an unsaturated compound having an acid group means a structural unit derived from the unsaturated compound in a copolymer obtained by polymerizing the unsaturated compound as a monomer. A copolymer having the structural unit can be obtained by polymerizing an unsaturated compound having an acid group as a monomer. Moreover, it can also be obtained by adding an acid anhydride to a copolymer having a structural unit having a hydroxy group.

Resin (A) preferably has a structural unit (Ac1).

As unsaturated compounds having an acid group, unsaturated carboxylic acids and unsaturated carboxylic anhydrides are preferable. Specific examples of unsaturated carboxylic acids and unsaturated carboxylic anhydrides include:

(meth)acrylic acid, crotonic acid, vinylbenzoic acid, methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methyl Bicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2 unsaturated monocarboxylic acids such as -ene, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene, and α-(hydroxymethyl)(meth)acrylic acid;

Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl unsaturated dicarboxylic acids such as tetrahydrophthalic acid, 1,4-cyclohexenedicarboxylic acid, and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene;

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride , unsaturated dicarboxylic acid anhydrides such as dimethyltetrahydrophthalic anhydride and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride (hymic acid anhydride);

Unsaturated mono[(meth)acryloyloxyalkyl] esters of bivalent or higher polyvalent carboxylic acids, such as mono[2-(meth)acryloyloxyethyl] succinic acid, mono[2-(meth)acryloyloxyethyl] phthalate, etc. ;

etc. can be mentioned.

Among these, (meth)acrylic acid and maleic anhydride are preferred because they are excellent in copolymerization reactivity and alkali solubility of the copolymer. These are used alone or in combination.

〔4〕 Composition unit (Ac2)

The structural unit (Ac2) is a different structural unit from the structural units (Aa), (Ab), and (Ac1). The structural unit (Ac2) is derived from a monomer polymerizable with a monomer from which other structural units (e.g., structural units (Aa), (Ab), or (Ac1)) are derived. As a specific example of such a monomer,

Methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, cyclo Hexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decan-8-yl(meth)acrylate (in the technical field, dicyclofentanyl (as the common name) (It is called meta)acrylate), tricyclo[5.2.1.0 ^2,6 ]decen-8-yl(meth)acrylate (in the technical field, it is called "dicyclopentenyl (meth)acrylate" as a common name) (It is called), dicyclopentanyloxyethyl (meth)acrylate, isobornyl (meth)acrylate,

(meth)acrylic acid esters such as phenyl (meth)acrylate, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and 2-hydroxypropyl (meth)acrylate;

Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconic acid;

Bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybi Cyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2 -N, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept Bicyclo unsaturated compounds such as -2-ene;

Dicarbonyl such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, and N-succinimidyl-4-maleimide butyrate. mead compounds;

Styrene compounds such as styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, and p-methoxystyrene;

(meth)acrylonitrile, vinyl chloride, vinylidene chloride, (meth)acrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, etc.

Among these, from the viewpoint of reactivity in copolymerization and heat resistance of the copolymer, (meth)acrylic acid ester, styrene compound, and dicarbonylimide compound are preferable, and methyl (meth)acrylate and n-butyl (meth)acrylic More preferred are cyclo[5.2.1.0 ^2,6 ]decan-8-yl(meth)acrylate, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide and N-benzylmaleimide. . These are used alone or in combination.

[5] Resin (A)

Resin (A) is the following resin [K1] or [K2].

Resin [K1]: A copolymer composed of a structural unit (Aa) and a structural unit (Ab);

Resin [K2]: A copolymer composed of a structural unit (Aa), a structural unit (Ab), and a structural unit (Ac).

Resin (A) is preferably resin [K2]. Furthermore, among the resin [K2], it is preferable that the structural unit (Ac) contains a structural unit (Ac1) and a structural unit (Ac2).

When the resin (A) contains a structural unit (Ac1), the ratio is preferably 1 to 50 mol%, more preferably 5 to 40 mol%, based on the total structural units constituting the resin (A).

When the resin (A) contains a structural unit (Ac2), the ratio is preferably 1 to 70 mol%, more preferably 5 to 60 mol%, based on the total structural units constituting the resin (A).

In the resin [K1], the ratio of each structural unit is, with respect to all structural units constituting the resin [K1],

Composition unit (Aa); 5 to 95 mol%

building block (Ab); It is preferably 5 to 95 mol%,

Composition unit (Aa); 30 to 70 mol%

building block (Ab); It is more preferable that it is 30 to 70 mol%.

If the ratio of the structural units constituting the resin [K1] is within the above range, it is preferable because the storage stability of the curable resin composition is excellent, the heat resistance and mechanical strength of the resulting film are excellent, and a cured film with excellent solvent resistance can be formed. do.

In the resin [K2], the ratio of each structural unit is, among all structural units constituting the resin [K2],

Composition unit (Aa); 5 to 80 mol%,

building block (Ab); 5 to 80 mol%,

Composition Unit (Ac); It is preferably 1 to 70 mol%,

Composition unit (Aa); 5 to 60 mol%,

building block (Ab); 5 to 60 mol%,

Composition Unit (Ac); 3 to 60 mol%

It is more preferable to be

In the case where the resin [K2] contains only the structural unit (Ac1) as the structural unit (Ac),

Composition unit (Aa); 5 to 80 mol%,

building block (Ab); 5 to 80 mol%,

Building unit (Ac1); It is preferably 5 to 40 mol%,

Composition unit (Aa); 5 to 50 mol%,

building block (Ab); 5 to 50 mol%,

Building unit (Ac1); It is more preferable that it is 10 to 40 mol%.

In the resin [K2], when it contains only the structural unit (Ac2) as the structural unit (Ac),

Composition unit (Aa); 5 to 80 mol%,

building block (Ab); 5 to 80 mol%,

Composition unit (Ac2); It is preferably 1 to 70 mol%,

Composition unit (Aa); 5 to 50 mol%,

building block (Ab); 5 to 50 mol%,

Composition unit (Ac2); It is more preferable that it is 3-60 mol%.

In the resin [K2], when the structural unit (Ac) contains both a structural unit (Ac1) and a structural unit (Ac2),

Composition unit (Aa); 5 to 50 mol%,

building block (Ab); 5 to 50 mol%,

Building unit (Ac1); 1 to 50 mol%,

Composition unit (Ac2); It is preferably 1 to 60 mol%,

Composition unit (Aa); 5 to 30 mol%,

building block (Ab); 5 to 30 mol%,

Building unit (Ac1); 10 to 40 mol%,

Composition unit (Ac2); It is more preferable that it is 3-55 mol%.

If the ratio of the structural units of the resin [K2] is within the above range, it is preferable in that a cured film can be obtained that has excellent storage stability of the curable resin composition, heat resistance and mechanical strength of the resulting film, and also has excellent solvent resistance.

The weight average molecular weight (Mw) of the resin (A) in terms of polystyrene is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, further preferably 5,000 to 30,000, and particularly preferably 5,000 to 20,000. If the weight average molecular weight (Mw) of the resin (A) is within the above range, the applicability of the curable resin composition of the present invention tends to be good and is preferable.

The dispersion degree [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the resin (A) is preferably 1.1 to 6.0, more preferably 1.2 to 4.0. When the degree of dispersion is within the above range, the resulting cured film tends to have better solvent resistance.

When the resin (A) contains a structural unit (Ac1), its acid value (converted to solid content) is preferably 30 mg-KOH/g or more and 180 mg-KOH/g or less, more preferably 40 mg-KOH/g. Not less than 150 mg-KOH/g or less, more preferably not less than 50 mg-KOH/g and not more than 135 mg-KOH/g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin, and can be obtained by titration using an aqueous potassium hydroxide solution. If the acid value of the resin (A) is within the above range, the resulting cured film tends to have excellent adhesion to the substrate.

Resin (A) can be obtained by polymerizing a monomer leading to the structural unit (Aa), a monomer leading to the structural unit (Ab), and, if necessary, a monomer leading to the structural unit (Ac).

Examples of the polymerization method include those described in the document "Experimental Methods for Polymer Synthesis" (written by Takayuki Otsu, published by Chemistry Co., Ltd., 1st edition, 1st printing, March 1, 1972).

Specifically, a monomer for deriving the structural unit (Aa), a monomer for deriving the structural unit (Ab), and, if necessary, a predetermined amount of a monomer for deriving the structural unit (Ac), a polymerization initiator, a solvent, etc. are added to the reaction vessel. For example, a method of replacing oxygen with nitrogen to create a deoxygenated atmosphere and heating and keeping the atmosphere warm while stirring is included.

In addition, by the polymerization method described above, a polymerization reaction is performed between the monomer deriving the monomer (Aa'), the monomer deriving the structural unit (Ab), and, if necessary, the monomer deriving the structural unit (Ac), and further Another example is a method of forming the structural unit (Aa) by reacting the structural unit (Aa') with the compound (Aa'').

In addition, the polymerization initiator and solvent in the production of resin (A) are not particularly limited, and those commonly used in the field can be used. Polymerization initiators include, for example, azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, etc.). Examples of the solvent may be any solvent that dissolves each monomer, and examples thereof include the solvents described later used in the curable resin composition.

In addition, the obtained resin may be used as a solution after the reaction, a concentrated or diluted solution may be used, or one taken out as a solid (powder) by a method such as reprecipitation may be used. In particular, by using the solvent used in the curable resin composition of the present invention as a polymerization solvent, the solution after the reaction can be used as is in the production of the curable resin composition, so the production process of the curable resin composition can be simplified.

The content of resin (A) in the curable resin composition of the present invention is preferably 5 to 95% by mass, more preferably 10 to 95% by mass, based on the solid content in the curable resin composition. If the content of the resin (A) is within the above range, the resulting cured film tends to have better solvent resistance. Here, the solid content in the curable resin composition refers to the component excluding the solvent from the curable resin composition. The total amount of solid content and the content of each component relative to this can be measured by known analytical means such as liquid chromatography or gas chromatography, for example.

<First additive>

The first additive is at least one compound selected from the group consisting of quaternary ammonium salts, quaternary phosphonium salts, and tertiary sulfonium salts.

[1] Quaternary ammonium salt

Examples of quaternary ammonium salts include compounds represented by formula (IV).

[In Formula (IV), R ⁴¹ to ^{R 44} each independently represent a hydrocarbon group having 1 to 24 carbon atoms which may have a substituent.

Y ^z- represents a z-valent negative ion.

z represents an integer from 1 to 3.]

Examples of the hydrocarbon group having 1 to 24 carbon atoms for R ⁴¹ to R ⁴⁴ include an alkyl group having 1 to 24 carbon atoms, a cycloalkyl group having 3 to 24 carbon atoms, an alkenyl group having 2 to 24 carbon atoms, a cycloalkenyl group having 3 to 24 carbon atoms, and 6 carbon atoms. Examples include an aryl group with ∼24 carbon atoms and an aralkyl group with 7 to 24 carbon atoms, preferably an alkyl group with 1 to 24 carbon atoms and an aryl group with 6 to 24 carbon atoms.

The total carbon number of R ⁴¹ to R ⁴⁴ per molecule of the compound represented by formula (IV) is preferably 4 to 100.

Substituents that the hydrocarbon group may have include a halogen atom, cyano group, acyl group, acyloxy group, carboxyl group, and alkoxy group.

Cations of the compound represented by formula (IV) include tetramethylammonium ion, tetraethylammonium ion, tetra-n-propylammonium ion, tetra-n-butylammonium ion, tri-n-octylmethylammonium ion, and hexadecyltrimethyl. Examples include ammonium ion, benzyltrimethylammonium ion, benzyltriethylammonium ion, hexadecylbenzyldimethylammonium ion, phenyltrimethylammonium ion and phenyltriethylammonium ion, preferably tetramethylammonium ion, tetraethylammonium ion, Examples include tetra-n-propylammonium ion, tetra-n-butylammonium ion, and tri-n-octylmethylammonium ion.

Examples of Y ^z- in formula (IV) include halide ions such as chlorine ions, fluorine ions, bromine ions, and iodine ions; sulfate ion, nitrate ion, phosphate ion, perchlorate ion, hydrogen sulfate ion and hydroxide ion; carboxylic acid ions such as acetic acid ion, benzoic acid ion, and salicylic acid ion; Sulfonic acid ions such as benzenesulfonic acid ion, p-toluenesulfonic acid ion, and trifluoromethanesulfonic acid ion; phenolate ions such as phenoxide ion and p-nitrophenoxide ion; Examples include tetrafluoroborate ions, hexafluorophosphate ions, and tetraphenyl borate ions, and preferably halide ions, carboxylate ions, sulfonic acid ions, and phenoxide ions.

The compound represented by formula (IV) is formed from any one selected from the above-mentioned cations and one selected from Y ^z- .

Quaternary ammonium ions other than the compound represented by formula (IV) include, for example, hexadecylpyridinium ion, N-dodecylpyridinium ion, N-benzyl-2-methylpyridinium ion, N,N, N,N',N',N'-hexamethyl-1,5-pentanediaminium ion and N,N,N,N',N',N'-hexamethyl-1,5-hexanediaminium ion, etc. can be mentioned.

The quaternary ammonium salt may be an intramolecular salt containing a carboxylic acid ion or a sulfonic acid ion in the molecule.

The quaternary ammonium salt is preferably a compound represented by formula (IV), and in the compound represented by formula (IV), it is more preferable that R ⁴¹ to ^{R 44} are independently an alkyl group having 1 to 24 carbon atoms, and the formula In the compound represented by (IV), it is more preferable that R ⁴¹ to ^{R 44} are independently alkyl groups having 1 to 6 carbon atoms. Quaternary ammonium salts include tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium salicylate, tetrabutylammonium nitrate, tetrabutylammonium hydrogen sulfate, tetrabutylammonium trifluoromethanesulfonate, tetrabutylammonium p-nitrophenoxide, and 3. -[Dimethyl(tetradecyl)ammonio]propane-1-sulfonate is more preferred.

[2] Quaternary phosphonium salt

Quaternary phosphonium salts include compounds represented by formula (V).

[In formula (V), R ⁵¹ to ^{R 54} each independently represent a hydrocarbon group having 1 to 24 carbon atoms.

Y ^y- represents a y-valent negative ion.

y represents an integer from 1 to 3.]

Examples of the hydrocarbon group having 1 to 24 carbon atoms for R ⁵¹ to R ⁵⁴ include an alkyl group with 1 to 24 carbon atoms, a cycloalkyl group with 3 to 24 carbon atoms, an alkenyl group with 2 to 24 carbon atoms, a cycloalkenyl group with 3 to 24 carbon atoms, and 6 carbon atoms. Examples include an aryl group with ∼24 carbon atoms and an aralkyl group with 7 to 24 carbon atoms, preferably an alkyl group with 1 to 24 carbon atoms and an aryl group with 6 to 24 carbon atoms.

Quaternary phosphonium ions in formula (V) include tetraethylphosphonium ion, tetra-n-butylphosphonium ion, tri-n-octylethylphosphonium ion, hexadecyltriethylphosphonium ion, and hexadecyltri. -n-butylphosphonium ion, n-butyltriphenylphosphonium ion, n-pentyltriphenylphosphonium ion, methyltriphenylphosphonium ion, benzyltriphenylphosphonium ion, tetraphenylphosphonium ion, etc. there is.

Examples of Y ^y- in formula (V) include the same anion as Y ^z- in formula (IV), and a halide ion is preferable.

As quaternary phosphonium salts, tetraethylphosphonium bromide, tetra-n-butylphosphonium chloride, and tetra-n-butylphosphonium acetate are preferred.

[3] Tertiary sulfonium salt

Tertiary sulfonium salts include compounds represented by formula (VI).

[In formula (VI), R ⁶¹ to ^{R 63} each independently represent a hydrocarbon group having 1 to 24 carbon atoms.

Y ^x- represents an x-valent negative ion.

x represents an integer from 1 to 3.]

The hydrocarbon group for R ⁶¹ to ^{R 63} includes an alkyl group with 1 to 24 carbon atoms, a cycloalkyl group with 3 to 24 carbon atoms, an alkenyl group with 2 to 24 carbon atoms, a cycloalkenyl group with 3 to 24 carbon atoms, and an aryl group with 6 to 24 carbon atoms. and aralkyl groups having 7 to 24 carbon atoms, and preferably an alkyl group having 1 to 24 carbon atoms and an aryl group having 6 to 24 carbon atoms.

Tertiary sulfonium ions in formula (VI) include, for example, di-n-butylmethylsulfonium ion, tri-n-butylsulfonium ion, dihexylmethylsulfonium ion, and dicyclohexylmethylsulfonium. ions and dodecylmethylethylsulfonium ions.

Y ^x- in formula (VI) includes the same anion as Y ^z- in formula (IV), and a halide ion is preferable.

As tertiary sulfonium salts, di-n-butylmethylsulfonium iodide, tri-n-butylsulfonium tetrafluoroborate and dodecylmethylethylsulfonium chloride are preferred.

The first additive is preferably a quaternary ammonium salt.

The content of the first additive is preferably 0.1 to 15 parts by mass, more preferably 0.5 to 10 parts by mass, and still more preferably 1 to 7 parts by mass, based on 100 parts by mass of the resin (A). If the content of the first additive is within the above range, the solvent resistance of the cured film formed from the curable resin composition containing it tends to improve more, so it is preferable.

<Second additive>

The second additive is at least one compound selected from the group consisting of epoxy compounds and 5-membered ring carbonate compounds.

[1] Epoxy compound

An epoxy compound is a compound having one or more, preferably two or more oxiranyl groups in one molecule.

The epoxy compound in the present invention preferably has a weight average molecular weight of less than 1000. The epoxy compound is preferably a compound having 10 or less oxiranyl groups, more preferably 6 or less.

In the curable resin composition of the present invention, the epoxy compound shown below is suitably used as the second additive.

[2] 5-membered ring carbonate compound

A 5-membered ring carbonate compound has at least one 5-membered ring carbonate structure, preferably two or more 5-membered ring carbonate structures, in the molecule.

Examples of five-membered ring carbonate compounds include 1,3-dioxolan-2-one, 4-butyl-1,3-dioxolan-2-one, 4,5-dimethyl-1,3-dioxolan-2-one, and allylsuccinic acid. Anhydride, 4-(meth)acryloyloxymethyl-1,3-dioxolan-2-one, 4-allyloxymethyl-1,3-dioxolan-2-one and 4-vinyloxymethyl-1,3 -dioxolane-2-one, etc. can be mentioned.

The second additive is preferably an epoxy compound.

The content of the second additive is preferably 0.1 to 100 parts by mass, more preferably 1 to 50 parts by mass, based on 100 parts by mass of the resin (A). If the content of the second additive is within the above range, the solvent resistance of the cured film formed from the curable resin composition containing it tends to improve more, so it is preferable.

The weight ratio of the first additive and the second additive is preferably 1:1 to 1:20, more preferably 1:1 to 1:10, and 1:1 to 1:5. It is more preferable to be

<Polymerizable Compound (C)>

The polymerizable compound (C) is not particularly limited as long as it is a compound that can be polymerized by active radicals generated from the polymerization initiator (D) by irradiation of light, etc., and examples include compounds having an ethylenically unsaturated bond. and, preferably, (meth)acrylic compounds.

Examples of the compound having one ethylenically unsaturated bond include compounds identical to the monomers from which each structural unit constituting the resin (A) is derived.

Compounds having two ethylenically unsaturated bonds include 1,3-butanediol di(meth)acrylate, 1,3-butanediol (meth)acrylate, 1,6-hexanediol di(meth)acrylate, and ethylene glycol di( Meth)acrylate, diethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol diacrylate , bis(acryloyloxyethyl)ether of bisphenol A, ethylene oxide modified bisphenol A di(meth)acrylate, propylene oxide modified neopentyl glycol di(meth)acrylate, ethylene oxide modified neopentyl glycol di(meth)acrylate. salt and 3-methylpentanediol di(meth)acrylate.

Compounds having three or more ethylenically unsaturated bonds include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, and ethylene. Oxide-modified trimethylolpropane tri(meth)acrylate, propylene oxide-modified trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate ) Acrylate, tripentaerythritol tetra(meth)acrylate, tripentaerythritol penta(meth)acrylate, tripentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth) ) Acrylate, reactant of pentaerythritol tri(meth)acrylate and acid anhydride, reactant of dipentaerythritol penta(meth)acrylate and acid anhydride, reactant of tripentaerythritol hepta(meth)acrylate and acid anhydride , caprolactone-modified trimethylolpropane tri(meth)acrylate, caprolactone-modified pentaerythritol tri(meth)acrylate, caprolactone-modified tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, caprolactone Modified pentaerythritol tetra(meth)acrylate, caprolactone modified dipentaerythritol penta(meth)acrylate, caprolactone modified dipentaerythritol hexa(meth)acrylate, caprolactone modified tripentaerythritol tetra(meth)acrylate, caprolactone modified Lactone-modified tripentaerythritol penta(meth)acrylate, caprolactone-modified tripentaerythritol hexa(meth)acrylate, caprolactone-modified tripentaerythritol hepta(meth)acrylate, caprolactone-modified tripentaerythritol octa(meth)acrylate , reactants of caprolactone-modified pentaerythritol tri(meth)acrylate and acid anhydride, reactants of caprolactone-modified dipentaerythritol penta(meth)acrylate and acid anhydride, and caprolactone-modified tripentaerythritol hepta(meth)acrylate. and reactants with acid anhydride.

As a compound having an ethylenically unsaturated bond, a compound having three or more ethylenically unsaturated bonds is preferable, and dipentaerythritol hexa(meth)acrylate is more preferable. These compounds may be used alone or in combination of two or more.

When the curable resin composition of the present invention contains a polymerizable compound (C), its content is preferably 20 to 200 parts by mass, more preferably 30 to 150 parts by mass, based on 100 parts by mass of the resin (A). When the content of the polymerizable compound (C) is within the above range, the strength, smoothness, and reliability of the cured film formed by curing the curable resin composition containing it tend to be good, so it is preferable.

<Polymerization initiator (D)>

The polymerization initiator (D) is not particularly limited as long as it is a compound that can initiate polymerization of the polymerizable compound (C) by generating active radicals, acids, etc. under the action of light or heat, and any known polymerization initiator can be used. .

The polymerization initiator (D) is preferably a polymerization initiator containing at least one selected from the group consisting of O-acyloxime compounds, alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, and biimidazole compounds. and, more preferably, a polymerization initiator containing an O-acyloxime compound.

When the polymerization initiator (D) is one of these polymerization initiators, the curable resin composition containing these has high sensitivity, and the transmittance in the visible light region of the cured film formed from the curable resin composition containing it tends to be high.

O-acyloxime compounds are compounds having a structure represented by formula (D1). Hereinafter, * represents a binding hand.

Examples of O-acyloxime compounds include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane-1- On-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6- (2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl- 2,4-dioxacyclopentanylmethyloxy)benzoyl}-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)- 9H-carbazol-3-yl]-3-cyclopentylpropan-1-imine and N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl] -3-cyclopentylpropan-1-one-2-imine. You may use commercially available products such as Irgacure (registered trademark) OXE01, OXE02 (manufactured by BASF Corporation), N-1919, NCI-831, and NCI-930 (manufactured by ADEKA Corporation).

An alkylphenone compound is a compound having a structure represented by formula (D2-1) or a structure represented by formula (D2-2). Among these structures, the benzene ring may have a substituent.

Compounds having a structure represented by formula (D2-1) include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4- Morpholinophenyl)-2-benzylbutan-1-one and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butane-1 -On can be mentioned. You may use commercially available products such as Irgacure (registered trademark) 369, 907, and 379 (above, manufactured by BASF Corporation). You may use a polymerization initiator having a group capable of causing chain transfer, which is described in Japanese Patent Publication No. 2002-544205. Compounds having a structure represented by formula (D2-2) include, for example, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4- (2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one Oligomers, α,α-diethoxyacetophenone, and benzyldimethylketal. In terms of sensitivity, a compound having a structure represented by the formula (D2-1) is preferable as the alkylphenone compound.

Examples of triazine compounds include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine and 2,4-bis(trichloromethyl)-6. -(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2- 1) ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine , 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine and 2,4-bis(trichloromethyl )-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. You may use a commercially available product such as Irgacure 819 (manufactured by BASF Japan Co., Ltd.).

Examples of biimidazole compounds include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichloro) Phenyl)-4,4',5,5'-tetraphenylbiimidazole (for example, see Japanese Patent Application Laid-Open No. 6-75372, Japanese Patent Application Laid-Open No. 6-75373, etc.), 2 ,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5 ,5'-tetra(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole (e.g. , Japanese Patent Application Laid-Open No. 48-38403, Japanese Patent Application Laid-Open No. 62-174204, etc.) and a ratio in which the phenyl group at the 4,4',5,5'-position is substituted by a carboalkoxy group. and imidazole compounds (for example, see Japanese Patent Application Laid-Open No. 7-10913, etc.).

Furthermore, examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; Benzophenone, o-benzoylbenzoic acid methyl, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, Benzophenone compounds such as 2,4,6-trimethylbenzophenone; Quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone, and camphorquinone; Examples include 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. These can be used in combination with the polymerization initiation aid (H) (especially amines) described later.

When the curable resin composition of the present invention contains a polymerization initiator (D), the content thereof is preferably 0.1 to 30 parts by mass, based on 100 parts by mass of the total content of the resin (A) and the polymerizable compound (C). Preferably it is 0.5 to 20 parts by mass, more preferably 5 to 20 parts by mass. When the content of the polymerization initiator (D) is within the above range, the cured film formed from the curable resin composition containing it has excellent solvent resistance and tends to have high visible light transmittance.

<Polymerization initiation aid (H)>

The polymerization initiation aid (H) is a compound or sensitizer used together with the polymerization initiator (D) to promote polymerization of the polymerizable compound (C), the polymerization of which was initiated by the polymerization initiator (D).

Examples of the polymerization initiation aid (H) include thiazoline compounds, amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.

Examples of the thiazoline compound include compounds represented by formulas (H1-1) to (H1-3), compounds described in Japanese Patent Application Laid-Open No. 2008-65319, and the like.

Amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, and 4-dimethylaminobenzoate 2. -Ethylhexyl, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 4,4'- Bis(ethylmethylamino)benzophenone etc. are mentioned, Among them, 4,4'-bis(diethylamino)benzophenone is preferable. You may use a commercially available product such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.).

Alkoxyanthracene compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and 9,10-dibutoxy. Anthracene, 2-ethyl-9,10-dibutoxyanthracene, etc. can be mentioned.

Thioxanthone compounds include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone. Santon, etc. can be mentioned.

Carboxylic acid compounds include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, and chlorophenyl alcohol. Examples include panylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

When the curable resin composition of the present invention contains a polymerization initiation aid (H), its content is preferably 0.1 to 30 parts by mass, based on 100 parts by mass of the total content of the resin (A) and the polymerizable compound (C), More preferably, it is 0.2 to 10 parts by mass. If the amount of the polymerization initiation aid (H) is within the above range, the sensitivity tends to be higher when forming a pattern from a curable resin composition containing it.

<Leveling Agent (B)>

Examples of the leveling agent (B) include silicone-based surfactants (however, they do not contain a fluorine atom), fluorine-based surfactants (however, they do not contain a silicon atom), and silicone-based surfactants containing a fluorine atom. These may have a polymerizable group in the side chain.

Examples of the silicone-based surfactant (however, it does not contain a fluorine atom) include surfactants having a siloxane bond in the molecule. Specifically, Toray Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (product name, Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324. , KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (manufactured by Momentive Performance Materials Japan Joint Stock Company). You can.

Examples of the above-mentioned fluorine-based surfactants (however, they do not contain silicon atoms) include surfactants having a fluorocarbon chain in the molecule. Specifically, Fluorad (registered trademark) FC430, FC431 (made by Sumitomo 3M Co., Ltd.), Megapak (registered trademark) F142D, F171, F172, F173, F177, F183, F554. , R30, RS-718-K (manufactured by DIC Co., Ltd.), FTOP (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Material Electronics Co., Ltd.), Surfron (Surflon) (registered trademark) S381, S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.), and E5844 (manufactured by Daikin Fine Chemical Laboratories Co., Ltd.).

Examples of the silicone-based surfactant having the above fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in the molecule. Specific examples include Megapak (registered trademark) R08, BL20, F475, F477, and F443 (manufactured by DIC Corporation).

As the leveling agent (B), a fluorine-based surfactant (however, it does not contain a silicon atom) is preferable.

When containing the leveling agent (B), its content rate is preferably 0.001 mass% or more and 0.2 mass% or less, more preferably 0.002 mass% or more and 0.1 mass% or less, and even more preferably, based on the solid content in the curable resin composition. is 0.005 mass% or more and 0.1 mass% or less.

<Solvent (E)>

The curable resin composition of the present invention may contain a solvent (E). The solvent (E) is not particularly limited, and solvents commonly used in the field can be used. For example, ester solvent (solvent containing -COO- in the molecule but not -O-), ether solvent (solvent containing -O- in the molecule but not -COO-), ether ester Solvent (solvent containing -COO- and -O- in the molecule), ketone solvent (solvent containing -CO- in the molecule but not -COO-), alcohol solvent (containing OH in the molecule, - solvents not containing O-, -CO-, and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, etc.

Ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyric acid. Butyl, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ-butyrolactone.

Ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, and propylene glycol. Monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1 , 4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetol and methyl anisole, etc. can be mentioned.

Ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, Ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-methoxy-2-methyl Methyl propionate, 2-ethoxy-2-methylethyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl Ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate.

Ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, and cyclopentane. cyclohexanone, cyclohexanone, and isophorone.

Examples of alcohol solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, and mesitylene.

Examples of amide solvents include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

Among the above solvents, organic solvents with a boiling point of 100 to 200°C at 1 atm are preferable in terms of coating properties and drying properties. Preferred solvents include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethylene glycol ethylmethyl ether, cyclohexanone, methoxybutanol, and methoxybutyl acetate. , propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethylene glycol ethyl methyl ether, methoxybutanol and methoxybutyl acetate are more preferable.

The content of solvent (E) in the curable resin composition of the present invention is preferably 60 to 95% by mass, more preferably 70 to 95% by mass, based on the total amount of the curable resin composition. In other words, the solid content of the curable resin composition of the present invention is preferably 5 to 40% by mass, more preferably 5 to 30% by mass. When the content of the solvent (E) is within the above range, the applicability of the curable resin composition tends to be good.

< Colorant (K) >

The curable resin composition of the present invention may contain a colorant (K). Colorants (K) include dyes and/or pigments. These may be used alone or in combination of two or more colorants, and in that case, any of the following may be used: a combination of only dyes, a combination of pigments only, or a combination of dyes and pigments.

The dye is not particularly limited, and known dyes can be used, and examples thereof include solvent dyes, acid dyes, direct dyes, and mordant dyes. Examples of dyes include compounds classified as having colors other than pigments in the color index (published by The Society of Dyers and Colourists) and known dyes described in dyeing notes (Shiki Sensha). In addition, according to the chemical structure, azo dye, cyanine dye, triphenylmethane dye, xanthene dye, phthalocyanine dye, anthraquinone dye, naphthoquinone dye, quinoneimine dye, methine dye, azomethine dye, squaryllium dye, Acridine dye, styryl dye, coumarin dye, quinoline dye, and nitro dye can be mentioned.

Specifically, C.I. Solvent Yellow 4 (hereinafter, the description C.I. Solvent Yellow will be omitted and only the number will be used), 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 117, 162, 163, 167, 189;

C.I. Solvent Red 45, 49, 111, 125, 130, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247;

C.I. Solvent Orange 2, 7, 11, 15, 26, 56, 77, 86;

C.I. Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60;

C.I. Solvent blue 4, 5, 14, 18, 35, 36, 37, 45, 58, 59, 59:1, 63, 67, 68, 69, 70, 78, 79, 83, 90, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139;

C.I. C.I. solvent green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35, etc. solvent dye,

C.I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 1 84, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;

C.I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 33, 34, 35, 37, 40, 42, 44, 50, 51, 52, 57, 66, 73, 76, 80, 87, 88, 91, 92, 94, 95, 97, 98, 103, 106, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 155, 158, 160, 172, 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 2 81, 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 388, 394, 401, 412, 417, 418, 422, 426;

C.I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;

C.I. Acid Violet 6B, 7, 9, 15, 16, 17, 19, 21, 23, 24, 25, 30, 34, 38, 49, 72, 102;

C.I. Acid Blue 1, 3, 5, 7, 9, 11, 13, 15, 17, 18, 22, 23, 24, 25, 26, 27, 29, 34, 38, 40, 41, 42, 43, 45, 48, 51, 54, 59, 60, 62, 70, 72, 74, 75, 78, 80, 82, 83, 86, 87, 88, 90, 90:1, 91, 92, 93, 93:1, 96, 99, 100, 102, 103, 104, 108, 109, 110, 112, 113, 117, 119, 120, 123, 126, 127, 129, 130, 131, 138, 140, 142, 143, 147 , 150, 151, 154, 158, 161, 166, 167, 168, 170, 171, 175, 182, 183, 184, 187, 192, 199, 203, 204, 205, 210, 213, 229, 234, 2 36, 242, 243, 256, 259, 267, 269, 278, 280, 285, 290, 296, 315, 324:1, 335, 340;

C.I. Acid Green 1, 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 25, 27, 28, 41, 50, 50:1, 58, 63, 65, 80, C.I.s such as 104, 105, 106, 109, etc. acid dye,

C.I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141;

C.I. Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;

C.I. Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;

C.I. Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;

C.I. Direct Blue 1, 2, 3, 6, 8, 15, 22, 25, 28, 29, 40, 41, 42, 47, 52, 55, 57, 71, 76, 77, 78, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 1 96, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 2 46, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293;

C.I. C.I. of Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, etc. direct dye,

C.I. Disperse Yellow 51, 54, 76;

C.I. Disperse Violet 26, 27;

C.I. C.I. such as Dispers Blue 1, 14, 56, 60, etc. disperse dye,

C.I. Basic Red 1, 10;

C.I. Basic Blue 1, 3, 5, 7, 9, 19, 21, 22, 24, 25, 26, 28, 29, 40, 41, 45, 47, 54, 58, 59, 60, 64, 65, 66, 67, 68, 81, 83, 88, 89;

C.I. Basic Violet 2;

C.I. Basic Red 9;

C.I. Basic Green 1; C.I., etc. basic dye,

C.I. Reactive Yellow 2, 76, 116;

C.I. Reactive Orange 16;

C.I. Reactive Red 36; C.I., etc. reactive dye,

C.I. Mordant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

C.I. Mordant Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 29, 30, 32, 33, 36, 37, 38 , 39, 41, 42, 43, 45, 46, 48, 52, 53, 56, 62, 63, 71, 74, 76, 78, 85, 86, 88, 90, 94, 95;

C.I. Mordaunt Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;

C.I. Mordaunt Violet 1, 1:1, 2, 3, 4, 5, 6, 7, 8, 10, 11, 14, 15, 16, 17, 18, 19, 21, 22, 23, 24, 27, 28 , 30, 31, 32, 33, 36, 37, 39, 40, 41, 44, 45, 47, 48, 49, 53, 58;

C.I. Mordant Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43 , 44, 48, 49, 53, 61, 74, 77, 83, 84;

C.I. C.I. of Mordaunt Green 1, 3, 4, 5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43, 53, etc. mordant dye,

C.I. Bat Green 1 and other C.I. Vat dye, etc. can be mentioned.

Additionally, dyes described in Japanese Patent Application Laid-Open No. 2010-32999, Japanese Patent Application Laid-Open No. 4492760, Japanese Patent Application Laid-Open No. 2013-50693, and Japanese Patent Application Laid-Open No. 2013-178478 can be mentioned.

These dyes can be appropriately selected according to the spectral spectrum of the desired color filter.

Examples of the above pigments include organic pigments and inorganic pigments, and pigments classified as pigments in the Color Index (published by The Society of Dyers and Colourists).

Pigments include, for example, C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129, 137, 138 , 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, 214, etc.;

C.I. Orange pigments such as Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, and 73;

C.I. Red pigments such as Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265 ;

C.I. Blue pigments such as Pigment Blue 15, 15:3, 15:4, 15:6, and 60;

C.I. Violet-colored pigments such as Pigment Violet 1, 19, 23, 29, 32, 36, and 38;

C.I. Green pigments such as Pigment Green 7, 36, 58, and 59;

C.I. Brown pigments such as Pigment Brown 23 and 25;

C.I. Black pigments such as pigment black 1 and 7 can be mentioned.

Among them, C.I. Pigment Yellow 138, 139, 150, C.I. Pigment Red 177, 242, 254, C.I. Pigment Violet 23, C.I. Pigment Blue 15:6 and C.I. It is preferred that it contains at least one pigment selected from Pigment Green 7, 36, 58, and 59. These pigments may be used individually or in combination of two or more types.

If necessary, the pigment is treated with rosin, surface treated using a pigment derivative with an acidic or basic group introduced, grafted onto the surface of the pigment with a polymer compound, atomized by a sulfuric acid atomizing method, or organically treated to remove impurities. Washing treatment using a solvent or water, or removal treatment using an ion exchange method of ionic impurities, etc. may be performed.

Examples of the pigment dispersants include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic surfactants. These may be used individually or in combination of two or more types. Specifically, the product names are KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Florene (manufactured by Kyoeisha Chemical Co., Ltd.), SOLSPERSE (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by CIBA Co., Ltd.), and Aji. Examples include AJISPER (manufactured by Ajinomoto Fine Techno Co., Ltd.) and Disperbyk (manufactured by BYK Chemistry Co., Ltd.).

When using a pigment dispersant, the amount used is preferably 1 part by mass or more and 100 parts by mass or less, more preferably 5 parts by mass or more and 50 parts by mass or less, based on 100 parts by mass of the total amount of pigment. If the amount of the pigment dispersant used is within the above range, a pigment dispersion in a uniformly dispersed state tends to be obtained.

When the curable resin composition of the present invention contains a colorant (K), its content is preferably 5 to 70% by mass, more preferably 8 to 65% by mass, and still more preferably 10 to 60% by mass, based on the total amount of solid content. It is mass%. If the content of the colorant (K) is within the above range, it can be adjusted to the desired chromaticity.

<Other ingredients>

The curable resin composition of the present invention may, if necessary, contain additives known in the art, such as fillers, other polymer compounds, antioxidants, ultraviolet absorbers, chain transfer agents, and adhesion promoters.

When the curable resin composition of the present invention does not contain a colorant, it is filled in a quartz cell with an optical path length of 1 cm, and the transmittance is measured using a spectrophotometer under the conditions of a measurement wavelength of 400 to 700 nm. The average transmittance is is preferably 70% or more, more preferably 80% or more.

When the curable resin composition of the present invention does not contain a colorant, the average transmittance of the cured film formed from the composition is preferably 90% or more, more preferably 95% or more. This average transmittance is the average value when measured using a spectrophotometer under the conditions of a measurement wavelength of 400 to 700 nm for a film with a thickness of 2 μm after heat curing (100 to 250°C, 5 minutes to 3 hours). Thereby, a cured film excellent in transparency in the visible light region can be provided.

[Method for producing curable resin composition]

The curable resin composition of the present invention includes a resin (A), a first additive and a second additive, a solvent (E) used as needed, a polymerizable compound (C), a polymerization initiator (D), and a polymerization initiation aid (H). ), leveling agent (B), colorant (K), and other components can be produced by mixing them by a known method. After mixing, it is preferable to filter through a filter with a pore diameter of about 0.05 to 5 ㎛.

[Method for producing cured film]

The cured film of the present invention can be manufactured by applying the curable resin composition of the present invention onto a substrate, drying it, and then heating it. More specifically, the method for producing a cured film of the present invention includes the following steps (1) to (3).

Process (1): A process of applying the curable resin composition of the present invention to a substrate,

Process (2): Process of drying the curable resin composition after application under reduced pressure and/or heat drying to form a composition layer,

Process (3): Process of heating the composition layer.

Moreover, when the curable resin composition of this invention contains a polymeric compound (C) and a polymerization initiator (D), a cured film with a pattern can be manufactured by performing the following process.

Process (1): A process of applying the curable resin composition of the present invention to a substrate,

Step (2): A step of drying the curable resin composition after application under reduced pressure and/or heat drying to form a composition layer,

Process (2a): Process of exposing the composition layer through a photomask,

Process (2b): Process of developing the composition layer after exposure,

Process (3a): A process of heating the composition layer after development.

Step (1) is a step of applying the curable resin composition of the present invention to a substrate (underlying substrate). Examples of the substrate include glass, metal, and plastic. A color filter, an insulating film, a conductive film, and/or a driving circuit, etc. may be formed on the substrate. Coating on the substrate is preferably performed using a coating device such as a spin coater, slit & spin coater, slit coater, inkjet, roll coater, or dip coater.

Step (2) is a step of drying the curable resin composition after application under reduced pressure and/or drying it by heat to form a composition layer. By performing this process, volatile components such as solvents in the curable resin composition are removed. Reduced pressure drying is preferably performed under a pressure of 50 to 150 Pa and a temperature range of 20 to 25°C. Heat drying (prebake) may be performed before or after reduced pressure drying. Heat drying is usually performed using a heating device such as an oven or hot plate. The temperature of heat drying is preferably 30 to 120°C, more preferably 50 to 110°C. Moreover, the heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes.

Process (3) is a process (post-bake) of heating the composition layer. Heating is usually performed using a heating device such as an oven or hot plate. The heating temperature is preferably 80 to 220°C, more preferably 90 to 200°C, and even more preferably 90 to 150°C. The heating time is preferably 1 to 120 minutes, more preferably 3 to 60 minutes. By performing heating under such conditions, a cured film having excellent solvent resistance can be obtained without deteriorating the properties of the substrate or the like.

Step (2a) is a step of exposing the composition layer formed in step (2) through a photomask. The photomask is one in which a light-shielding portion is formed corresponding to the portion of the composition layer to be removed. The shape of the light-shielding portion is not particularly limited and can be selected depending on the intended use. The light source used for exposure is preferably a light source that generates light with a wavelength of 250 to 450 nm. For example, light below 350 nm can be cut using a filter that cuts this wavelength range, or light around 436 nm, 408 nm, and 365 nm can be cut using a bandpass filter that extracts these wavelength ranges. You can use it to selectively extract it. Light sources include mercury lamps, light-emitting diodes, metal halide lamps, and halogen lamps. It is preferable to use an exposure device such as a mask aligner or stepper because it allows uniform irradiation of parallel light to the entire exposure surface and accurate alignment of the photomask and the composition layer.

Step (2b) is a step of developing the composition layer after exposure. By developing the composition layer after exposure by contacting it with a developer, the unexposed portion of the composition layer is dissolved in the developer and removed, thereby forming a composition layer with a pattern on the substrate. The developing solution is preferably an aqueous solution of an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, or tetramethylammonium hydroxide. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10 mass%, more preferably 0.03 to 5 mass%. Additionally, the developer may contain a surfactant. The development method may be any of the paddle method, dipping method, and spray method. Additionally, the substrate may be tilted at an arbitrary angle during development. It is desirable to wash with water after development.

Step (3a) is a step of heating the composition layer after development. By performing heating in the same manner as the above step (3), the composition layer having a pattern is cured, and a cured film having a pattern is formed on the substrate.

According to the curable resin composition of the present invention, a cured film having excellent solvent resistance can be produced even when curing at low temperatures, such as 140°C to 150°C. The cured film is useful as a photo spacer, overcoat, and interlayer insulating film used in display devices. Moreover, when the curable resin composition of the present invention contains a colorant, it is useful as a color filter used in display devices such as liquid crystal displays, organic EL devices, and electronic paper, and solid-state imaging devices.

[Example]

Below, the present invention will be explained in more detail by way of examples. “%” and “part” in the examples mean mass% and mass part, unless otherwise specified.

(Synthesis Example 1: Synthesis of copolymer (a1))

80 parts of propylene glycol monomethyl ether was introduced into a flask equipped with a stirring blade, a reflux condenser, a thermometer, and a dropping funnel, and heated to 90°C. Mix 41.3 parts of vinyl toluene, 26.6 parts of 2-(1,3-dioxobutyloxy)ethyl methacrylate, 27.1 parts of methacrylic acid, 5 parts of azobis (isobutyronitrile), and 30 parts of propylene glycol monomethyl ether. The solution was started to be continuously dropped into the flask by means of a dropping funnel. The temperature inside the flask during the dropwise addition of the mixed solution was maintained at 90 ± 1°C, and the dropwise addition was completed in 3 hours. After completion of dropping, the temperature inside the flask was set to 90 ± 1°C and maintained for 6 hours. After the reaction, the reaction solution was cooled to 40°C or lower, and 0.12 parts of 4-methoxyphenol, 22.6 parts of 3,4-epoxycyclohexylmethyl acrylate, 4.7 parts of triphenylphosphine, and 90 parts of propylene glycol monomethyl ether were added. was added and the temperature inside the flask was raised to 110°C, and then an addition reaction was performed at a temperature inside the flask of 110 ± 1°C to obtain a copolymer (a1) solution with a solid content of 36.5%. The weight average molecular weight (Mw) of copolymer (a1) was 16,500, the degree of dispersion was 2.4, and the acid value in terms of solid content was 92 mg-KOH/g. Copolymer (a1) has the following structural units.

(Synthesis Example 2: Synthesis of copolymer (a2))

70 parts of propylene glycol monomethyl ether was introduced into a flask equipped with a stirring blade, a reflux condenser, a thermometer, and a dropping funnel, and heated to 90°C. Dicyclopentanyl methacrylate 52.6 parts, 2-(1,3-dioxobutyloxy)ethyl methacrylate 20.7 parts, methacrylic acid 26.7 parts, azobis(isobutyronitrile) 5 parts, propylene glycol monomethyl ether 30 parts of the mixed solution was continuously dropped into the flask using a dropping funnel. The temperature inside the flask during the dropwise addition of the mixed solution was maintained at 90 ± 1°C, and the dropwise addition was completed in 3 hours. After completion of dropping, the temperature inside the flask was maintained at 90 ± 1°C for 6 hours. After reaction, the reaction solution was cooled to 40°C or lower, and 0.12 parts of 4-methoxyphenol, 17.6 parts of 3,4-epoxycyclohexylmethyl acrylate, 4.7 parts of triphenylphosphine, and 85 parts of propylene glycol monomethyl ether were added. was added and the temperature inside the flask was raised to 110°C, and then an addition reaction was performed at a temperature inside the flask of 110 ± 1°C to obtain a copolymer (a2) solution with a solid content of 37.9%. The weight average molecular weight (Mw) of the obtained copolymer (a2) was 14,300, the degree of dispersion was 2.4, and the acid value in terms of solid content was 103 mg-KOH/g. Copolymer (a2) has the following structural units.

(Synthesis Example 3: Synthesis of copolymer (a3))

70 parts of propylene glycol monomethyl ether was introduced into a flask equipped with a stirring blade, a reflux condenser, a thermometer, and a dropping funnel, and heated to 90°C. 44.6 parts of methyl methacrylate, 28.6 parts of 2-(1,3-dioxobutyloxy)ethyl methacrylate, 26.8 parts of methacrylic acid, 5 parts of azobis (isobutyronitrile), 30 parts of propylene glycol monomethyl ether. The mixed solution was started to be continuously dropped into the flask using a dropping funnel. The temperature inside the flask during the dropwise addition of the mixed solution was maintained at 90 ± 1°C, and the dropwise addition was completed in 3 hours. After completion of dropping, the temperature inside the flask was maintained at 90 ± 1°C for 6 hours. After the reaction, the reaction solution was cooled to 40°C or lower, and 0.12 parts of 4-methoxyphenol, 24.4 parts of 3,4-epoxycyclohexylmethyl acrylate, 5 parts of triphenylphosphine, and 95 parts of propylene glycol monomethyl ether were added. was added and the temperature inside the flask was raised to 110°C, and then an addition reaction was performed at a temperature inside the flask of 110 ± 1°C to obtain a copolymer (a3) solution with a solid content of 38.5%. The weight average molecular weight (Mw) of the obtained copolymer (a3) was 15,800, the degree of dispersion was 2.4, and the acid value in terms of solid content was 80 mg-KOH/g. Copolymer (a3) has the following structural units.

(Synthesis Example 4: Synthesis of Resin (a))

100 parts of propylene glycol monomethyl acetate was introduced into a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, and the temperature was raised to 120°C by stirring while purging with nitrogen. Next, a mixture of 43 parts of methyl methacrylate, 25 parts of methacrylic acid, and 0.68 parts of tert-butylperoxy-2-ethylhexanoate (Perbutyl O; manufactured by Nichiyu Co., Ltd.) is poured 2 times from the dropping funnel. It was added dropwise to the flask over time, and further stirred at 120°C for 2 hours to obtain a copolymer. Next, the inside of the flask was purged with air, and 10 parts of glycidyl methacrylate, 0.44 parts of triphenylphosphine, and 0.08 parts of methylhydroquinone were added to the copolymer solution, and the reaction was continued at 120°C until the solid acid value was 100. The reaction was terminated at mg-KOH/g. By adding 50 parts of propylene glycol monomethyl acetate to this, a solution of resin (a) with a solid content of 40% was obtained. The weight average molecular weight (Mw) of resin (a) was 30,000, the degree of dispersion was 2.5, and the acid value in terms of solid content was 100 mg-KOH/g. Resin (a) has the following structural units.

The weight average molecular weight (Mw) and number average molecular weight (Mn) of the obtained resin were measured using the GPC method under the following conditions.

Device: HLC-8120GPC (manufactured by Tosoh Corporation)

Column: TSK-GEL G2000HXL

Column temperature: 40℃

Solvent: THF (tetrahydrofuran)

Flow rate: 1.0 mL/min

Solid content concentration of test liquid: 0.001 to 0.01 mass%

Injection volume: 50 μL

Detector: RI

Standard materials for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Co., Ltd.)

The ratio (Mw/Mn) of the weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of polystyrene obtained above was referred to as the degree of dispersion.

(Synthesis Example 5: Synthesis of the compound represented by formula (A-IV))

20 parts of the compound represented by formula (1x) and 200 parts of N-propyl-2,6-dimethylaniline (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed under light-shielding conditions, and the resulting solution was stirred at 110°C for 6 hours. After cooling the obtained reaction liquid to room temperature, it was added to a mixture of 800 parts of water and 50 parts of 35% hydrochloric acid and stirred at room temperature for 1 hour, and crystals precipitated. The precipitated crystals were collected as a residue after suction filtration and dried to obtain a compound represented by formula (A-IV).

Identification of the compound represented by formula (A-IV)

(Mass spectrometry) Ionization mode = ESI+: m/z = [M+H] ⁺ 659.3

Exact Mass: 658.3

[Examples 1 to 19, 21 to 23, Comparative Examples 1 and 2]

<Preparation of curable resin composition>

Each component shown in Table 1 is contained in the ratio shown in Table 1, and the solvent (E) of each curable resin composition is a mixed solvent of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether (mixing ratio is 1:1 in mass ratio). ), and further mixed to obtain the solid concentration shown in Table 1 to obtain a curable resin composition.

In Table 1, the parts of each component represent the mass parts converted to solid content.

Copolymer (a1): Copolymer obtained by Synthesis Example 1

Copolymer (a2): Copolymer obtained by Synthesis Example 2

Copolymer (a3): Copolymer obtained by Synthesis Example 3

Resin (a): Resin obtained by Synthesis Example 4

(x1): Tetrabutylammonium chloride

(x2): Tetrabutylammonium p-nitrophenoxide

(x3): tetrabutylammonium bromide

(x4): tetrabutylammonium salicylate

(x5): tetrabutylammonium nitrate

(x6): Tetrabutylammonium trifluoromethanesulfonate

(x7): Tetrabutylammonium hydrogen sulfate

(x8): 3-[dimethyl(tetradecyl)ammonio]propane-1-sulfonate (above, manufactured by Tokyo Chemical Industry Co., Ltd.)

(y1): Compound represented by the following formula (ED-529; manufactured by ADEKA Co., Ltd.)

(y2): Compound represented by the following formula (DA-MGIC; manufactured by Shikoku Chemical Industry Co., Ltd.)

(y3): Compound represented by the following formula (MA-DGIC; manufactured by Shikoku Chemical Industry Co., Ltd.)

(y4): Compound represented by the following formula (TEPIC (registered trademark); manufactured by Nissan Chemical Industries, Ltd.)

(y5): Compound represented by the following formula (S-184; manufactured by SYNASIA)

(y6): Compound represented by the following formula (TG-G; manufactured by Shikoku Chemical Industry Co., Ltd.)

(y7): Compound represented by the following formula (S-500; manufactured by SYNASIA)

(y8): Compound represented by the following formula (S-186; manufactured by SYNASIA)

(y9): Compound represented by the following formula (S-400; manufactured by SYNASIA)

(f1): Fluorine-based leveling agent (Megapak (registered trademark) F554; manufactured by DIC Co., Ltd.)

< Production of cured film 1 >

A 2-inch-by-2-inch glass substrate (Eagle On this substrate, the curable resin composition was spin-coated so that the post-baked film thickness was 1.5 μm. Next, it was dried under reduced pressure using a reduced pressure dryer (manufactured by VCD Microtech Co., Ltd.) until the degree of reduced pressure reached 66 Pa under the conditions of a rotary pump rotation speed of 1000 rpm, a booster pump rotation speed of 700 rpm, and a room temperature of 25°C. . After that, a cured film was obtained by baking at 140°C for 3 minutes on a hot plate.

< Solvent resistance evaluation >

The obtained cured film was immersed in propylene glycol monomethyl ether acetate at 23°C for 3 minutes and then thoroughly washed with water. The film thickness before immersion and after water washing (the film thickness before immersion is t1, and the film thickness after water washing is t2) was measured, and the ratio of the film thickness after water washing to the film thickness before immersion (t2/t1) was calculated. . In addition, a film thickness measuring device (DEKTAK XT; manufactured by Nippon Vacuum Technology Co., Ltd.) was used to measure the film thickness. The results are shown in Table 1.

[Example 20]

<Preparation of curable resin composition>

C.I. Pigment Blue 15:6 23.5 parts

8.2 parts of acrylic pigment dispersant, and

Propylene glycol monomethyl ether acetate 193 parts

Mix, sufficiently disperse the pigment using a bead mill, and then,

6.2 parts of compound (dye) represented by formula (A-IV)

Copolymer (a1) 60 parts (converted to solid content)

Dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 40 parts

Polymerization initiator (NCI-930; manufactured by ADEKA Co., Ltd.; O-acyloxime compound)

Part 16

2 copies of the above (x1)

Part 6 of (y6) above

Diacetone alcohol 20 parts

783 parts of propylene glycol monomethyl ether acetate, and

Leveling agent 0.1 part

was mixed to obtain a curable resin composition.

< Production of cured film 2 >

The curable resin composition was applied by spin coating on a 5 cm x 5 cm glass substrate (Eagle 2000, manufactured by Corning), and then prebaked at 100°C for 3 minutes to obtain a composition layer. After cooling, the distance between the substrate on which the composition layer was formed and the quartz glass photomask was set to 100 ㎛, and an exposure dose of 80 mJ/cm2 (365 mJ/cm2) was applied using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) under an air atmosphere. irradiated with light (nm standard). As a photomask, a photomask with a 1:1 line and space pattern of 100 ㎛ was used. The composition layer after light irradiation was developed by immersing it in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23°C for 60 seconds, and after washing with water, it was baked on a hot plate at 150°C for 5 minutes. By doing so, a cured film having a pattern was obtained.

The cured film produced from the curable resin composition of Example 20 by the method of Production 2 of the cured film was evaluated for solvent resistance in the same manner as above, and as a result, (t2/t1) was 1.

According to the present invention, a curable resin composition capable of forming a cured film excellent in solvent resistance can be provided, and the cured film is suitable for display devices, etc.

Claims (4)

Resin (A), which is a copolymer comprising a structural unit (Aa) having an α,β-unsaturated carbonyl group, a structural unit (Ab) having an active methylene group or an active methine group, and a structural unit (Ac1) derived from an unsaturated compound having an acid group. and,
Quaternary ammonium salts,
Contains an epoxy compound,
A curable resin composition wherein the unsaturated compound having an acid group is (meth)acrylic acid. According to claim 1,
A curable resin composition in which the epoxy compound is an epoxy compound having at least two oxiranyl groups in one molecule. A cured film formed from the curable resin composition according to claim 1 or 2. delete